Linear polyamides having high glass transition temperature prepared 4-(3-amino-propoxy)-phenyl-3-propylamine

ABSTRACT

A linear polyamide having a high glass transition temperature composed essentially of monomer units randomly distributed in the polymer chain, said monomer units having the formula   OR   WHEREIN R is a member selected from the group consisting of aliphatic, aromatic and aliphatic-aromatic radicals.

22] Filed:

United States Patent [191 Ando et al.

[54] LINEAR POLYAMIDES HAVING HIGH GLASS TRANSITION TEMPERATURE PREPARED4-(3-AMINO-PROPOXY)- PHENYL-S-PROPYLAMINE [75] Inventors: Tadanao Ando,Hiyog'o; Seiichi Kataoka; lsao Shiihara, both of Osaka, all of Japan[73] Assignee: Agency of Industrial Science 8:

' Technology, Tokyo, Japan Oct. 6, 1971 [21] Appl. No.: 187,174

' Related U.S. Application Data [63] Continuation-impart of Ser. No.870,673, Dec. 24,

1969, abandoned.

[52] U.S. Cl. ..260/47 CZ, 260/33.4 P, 260/78 R [51] Int. Cl. ..C08g20/20 [58] Field of Search ..260/47 CZ, 78

[56] References Cited UNITED STATES PATENTS 3,197,434 7/1965 Prestonetal ..260/47 Apr. 3, 1973 3,206,438 9/1965 Jamison ..260/78 PrimaryExaminerWilliam H. Short Assistant Examiner-L. L. Lee

Attorney-Kurt Kelman s7 ABSTRACT wherein R is a member selected from thegroup consisting of aliphatic, aromatic and aliphatic-aromatic radicals.

1 Claim, No Drawings LINEAR POLYAMIDES HAVING HIGH GLASS TRANSITIONTEMPERATURE PREPARED 4-(3- AMINO-PROPOXYHIIENYU3-PROPYLAMINE Thisapplication for U.S. Letters Patent is a continuation-in-part ofapplication Ser.'No. 870,673, filed Dec. 24, 1969, now abandoned.

This invention relates to a linear polyamide having a high glasstransition temperature.

Polyamides containing aromatic nuclei can be classified into two groups,one of which contains nomethylene group in the main chain thereof, andthe other containing methylene groups in said main chain. The polyamidein accordance with the present invention falls within the latter group.Typical well-known poly-amides of the latter group includepolyhexamethylene terephthalamide (Nylon 6T), poly-m-xyeasily availableat low cost as a by-product of the petroleum chemical industry.

The novel polyamide can easily be prepared industrially by carrying outheat-condensation of 4-(3- aminopropoxy)-phenyl-3-propylamine [H N-(CH,)-O

- -C,,H (Cl-l NH as a diamine constituent with a dicarboxylic acidhaving the formula HOOC-R-COOH or an ester thereof, wherein R representsan aliphatic, aromatic or aliphatic aromatic residual radical.4-(3aminopropoxy)-phenyl-3propylarnine used as a starting material inthe process for producing the poylamide of this invention can beprepared by, for example, reacting phenol with acrylonitrile in thepresence of a Lewis acid to obtain 4-oxyphenyl-propionitrile which isfurther reacted with an additional 1 mole of acrylonitrile in thepresence of a basic catalyst, for example, tetramethyl ammoniumhydroxide, trimethylbenzyl ammonium hydroxide, etc. to produce 4-(2-cyanoethoxy)phenyl-Z-propionitrile, and catalytically hydrogenating thethus obtained 4-(2-cyanoethoxy)phenyl-2-propionitrile in the presence ofRaney nickel or Raney cobalt catalyst under hydrogen pressure. Thisprocedure permits the production of 4-(3-aminopropoxy)-phenyl-3-propylamine in high yield and, further, can beadvantageously carried out on a commercial basis because the rawmaterials such as phenol and acrylonitrile are easily available at lowcost as a by-product in the petroleum chemical industry.

The other raw material, dicarboxylic acids, used in producing thepolyamide of the present invention may be any of the aliphatic(ii-dicarboxylic acids, aromatic dicarboxylic acids oraliphatic-aromatic dicarboxylic acids, for example, adipic acid, pimelicacid, su beric acid, azelaic acid, sebacic acid, decamethylene-l,ldicarboxylic acid, terephthalic acid, isophthalic acid,

l,4-bis(carbomethoxy)benzene, 4,4-dicarboxydiphenoxy-l ,2-ethane,4,4'-dicarboxydiphenoxy-l ,4- butane, and the like. Dimethyl esters,diethyl esters, diphenyl esters, di-acid chlorides, etc. of the abovedicarboxylic acids can also be used as raw materials of this invention.

The condensation-polymerization can be carried out by mixing the above4-(3-aminopropoxy)-phenyl-3- propylamine and an equimolar amount of thedicarboxylic acid or an ester therof (an amount of 5 percent over orbelow the equimolar amount is acceptable) and heating the resultingmixture at a temperature of from 180C to 300C for a period of from 1 to30 hours thereby effecting the condensation-polymerization reaction toproduce a polyamide polymer.

. At reaction temperatures below 180C the 4-(3-aminopropoxy)phenyl-3-propylamine, although a liquid at roomtemperature, forms a polyamide intermediate with the dicarboxylic acidand there is no or very slow further reaction between the startingmaterials. At a temperature above 300C, a decomposition reaction and thecondensation reaction take place simultaneously thereby decreasing thedegree of polymerization.

A reaction period of from 1 to 2 hours is adequate when the reaction isconducted on a laboratory scale, but the reaction usually requires about30 hours when a large amount of raw materials are used on a commercialscale.

The condensation-polymerization may be carried out in an inert solventsuch as water, alcohols or phenols including cresols and xylenols.

It is possible to control the degree of polymerization of the formedpolymer in the conventional manner'by the addition of an appropriateamount of a mono-functional compound or a dicarboxylic acid to thereaction system. The former compound includes, for example, amonocarboxylic acid such as acetic acid, benzoic acid and the like, anda primary amine such as monomethyl amine, monoethyl amine and the like,and the latter includes adipic acid, sebacic acid and the like.

The degree of polymerization is increased when thecondensation-polymerization reaction is conducted under normal pressureor pressurized conditions at an earlier stage of the reaction and underreduced pressure at a later stage of the reaction. Also, the reactionshould be carried out in an inert gas such as steam, carbon dioxide,nitrogen, hydrogen, argon, etc. so as to avoid the appearance of colorin the desired reaction product due to oxidation by air.

Alternatively, a solution of the starting material 4-(3-aminopropoxy)-phenyl-3 propylamine dissolved in alcohol or water can bemixed with an approximately equimolar amount of the dicarboxylic acid oran alcoholic solution thereof to produce a polyamide intermediate, i.e.,a salt complex which is then isolated and, if necessary, purified andthereafter subjected to the condensation-p0lymerization under the sameconditions as above.

Also, the polymer can be produced by the interfacialcondensation-polymerization method which comprises mixing, whilestirring, a solution of the dicarboxylic acid dichloride in awater-immiscible inert solvent with.

an aqueous solution of a hydrochloric acid acceptor such as sodiumhydroxide, into which has been dissolved the diamine starting materialor by the low-temperature solution polymerization method which comprisesreacting the diamine starting material with the dicarboxylic aciddichloride separately dissolved in a solvent which is inert for therespective reactant such as, for example, dimethylformamide,dimethylacetamide and the like, either in the presence or the absence ofa hydrochloric acceptor such as triethylamine.

The polymer obtained by the method described above is formed by thecondensation reaction of diamine containing one paraoxyphenylene groupwith dicarboxylic acid. As in this reaction dicarboxylic acid can freelyconnect with either the amino group in the head position or the aminogroup in the tail position of the diamine, the following twocombinations are possible:

Consequently, the polymer of the present inventions comprises a chain ofunits and units wherein the imino-propoxy radical, NI'l(Cl-l in thelatter units may face randomly to the left and right on the p-phenyleneradical. This polymer, however, is crystalline and is a resinoussubstance and is moreover characterized in that it melts at a relativelylow temperature. Although the polymer is rich in benzene nuclei in themain chainthereof, said polymer has a relatively low melting temperaturewhich makes it possible to easily effect molding of the molten polymer.This is due to the molecular structure of said polymer in which themonomer units are randomly distributed in said polymer chain.Accordingly, the polymer can be fabricated into a film having a hightenacity, or can be melt-spun into a fiber having a high stiffness inthe usual manner.

The features of the polymer prepared from 4-(3-aminopropoxy)-phenyl-3-propylamine and various dicarboxylic acids areshown in Table 1 below.

TABLE 1 Dicarboxylic Acid or Derivative Thereof Appearance Melting GlassPoint Transition (C)"' Temp. ("C)" Adipic Acid light yellow, I99 87opaque, stiff Sebacic Acid milk-white, 182 88 opaque, stiffDecamethylene-l ,10- lightly colored, 160 dicarboxylic Acid opaqueTerephthalic Acid milk-white, 275 100 opaque lsophthalic Acid colorless,121

transparent 4,4-Dicarboxymilk-white, 267 100 diphenoxy-l ,Z-ethaneopaque The temperature at which distinct vision of the spherulilcdisappearsis measured by means of a polarizing microscope and isconsidered as a melting temperature.

5 Measured by the dilatometer method.

The polymer of the present invention shows high glass-transitiontemperature quite superior to that of conventional aliphatic polyamides,for example, Nylon 66. This is due to the fact that the polymer of thisinvention contains both benzene nuclei derived from the diamineconstituents and oxygen bonds in the main chain thereof.

Since a resin generally does not vary in its mechanical characteristicat temperatures under its glass transition temperature, a resin having ahigh glass transition temperature such as the polymer of this inventionshows a relatively high modulus of elasticity and a socalled highstiffness property, and is additionally superior in impact resistance.

The polyamide of this invention was found to be superior in dyeingproperties for acid dyes as compared with conventional Nylon and wasproved to be an extremely useful substance for the production of fibersand films.

The following examples illustrate the present invention but are not tobe construed as a limitation of the scope of this invention.

EXAMPLE 1 A solution of 20.8g (0.l mole) of 4-(3-aminopropoxy)phenyl-3-propylamine dissolved in 200 ml of ethanol was mixed with asolution of 14.6g (0.1 mole) of adipic acid dissolved in 500 m1 ofethanol and allowed to stand to give a crystalline precipitate of thepolyamide intermediate having a melting point of 141 to 145C. 7 .09g(0.02 mole) of the thus obtained intermediate, 0.0l22g (0.000l mole) ofbenzoic acid and 1.5 ml of water were charged into a stainless steelpressure container which was then purged with nitrogen gas to make anitrogen atmosphere and sealed. The reaction was effected by immersingthe container in an oil bath at 240C, and after 3 hours the pressure wasgradually reduced by discharging the gas from the container whilemaintaining that temperature, and the reaction mixture was thenheat-treated for an additional 5 hours under the reduced pressure toyield a resinous substance which was light yellow in color, opaque and0a high stiffness. The polymer showed a limiting viscosity number of0.67 as measured in m-cresol solution at 25C and can be used for theformation of film and melt-spinning.

A polymer having the same quality as above was obtained when theprocedure described in Example 1 was repeated under the same conditionsbut substituting a hydrogen or carbon dioxide gas for the nitrogen gas.

EXAMPLE 2 A solution of 38.1g (0.183 mole) of 4-(3 a'minopropoxy)phenyl-3-propylamine dissolved in 200 ml of ethanol was mixed with asolution of 37.0g (0.183 mole) of sebacic acid dissolved in 800 ml ofethanol, and the resulting mixture was allowed to stand to give acrystalline precipitate of the polyamide intermediate having a meltingpoint of 176 to 177C. To 11.5. 2g of the thus obtained intermediate wasadded 0.0084 mg of acetic acid in a 0.04 molar water solution, and themixture was charged into a pressure container which was then purged withnitrogen gas to make .a nitrogen atmosphere and thereafter sealed. Thereaction was effected for 5 hours immersing the container in an oil bathat 220i 5C, and thereafter the pressure was reduced slowly over a periodof one hour while maintaining that temperature. The pressure was furtherreduced to about 30mrnl-lg where the reaction mixture was heat-treatedfor an additional hours to yield a resinous substance which wasmilk-white and opaque and of high stiffness, having a limiting viscositynumber of 1.06 (as measured in an m-cresol solution at C). The X-raydiffraction pattern of the resulting polymer exhibited a specific onedue to the crystalline highpolymer. The polymer had a meltingtemperature of 182C and was useful for the formation of film and formelt-spinning. For example, the fibers obtained by melt-spinning thepolymer through a single-hole nozzle at 195C was drawn to eight timesits original length in an air bath at 60C to give the fibers having afineness of 4.8 denier, a tensile strength of 4.52g/den., 29 percentelongation, and an initial modulus of eslasticity of 290 Kg/mm Thesefibers exhibited the same degree of dyeability for acid dyes as Nylon 6and were highly resistant to sunlight and ultraviolet irradiation. Noyellowing, as is commonly observed in such fibers, was observed, evenafter exposure to natural light for a period of more than one year.

EXAMPLE 3 20.83g of the distilled 4-(3-aminopropoxy)phenyl-3-propylamine (b.p., 158 to 162C/1.0 mmHg), 20.22g of sebacic acid, 0.061g of benzoic acid and 5 ml of water were charged into a pressurecontainer, which was then purged with nitrogen gas to make a nitrogenatmosphere and sealed. lt 'was then heated in'an oil bath having atemperature of 220C for 5 hours, after which the'pressure in thecontainer was reduced by slowly discharging the gas; then the reactionmixture was further heat-treated under the reduced pressure to effectthe condensation-polymerization. The polymer obtained had substantiallythe same quality as that obtained in Example 2.

EXAMPLE 4 EXAMPLE 5 1.041g of the distilled 4-(3-aminopropoxy)phenyl-3-propylamine, 5 m1 of methanol and 0.971 g of terephthalic acid dimethylester were charged into a closed container ,which had been purged withnitrogen gas, and heated by gradually raising the temperature to 240Cwhere the mixture was maintained for 2 hours. The pressure in thecontainer was then reduced by dischargin the gas while keeping thattemperature and then further reduced to about mmI-lg where the mixturewas heat-treated for 1 hour to give a colorless transparent resin.

A polymer can also be obtained following the same procedure as above butusing isophthalic acid diethyl ester in place of the terephthalic aciddimethyl ester.

EXAMPLE 6 4.75g of the distilled 4-(3-aminopropoxy) phenyl-3-propylamine, 3.80g of the ground pure terephthalic acid and 10 ml ofdistilled water were charged into a pressure container which was thenpurged with nitrogen gas to make a nitrogen atmosphere and sealed. Thetemperature of the container was then raised to 240C and, after 30minutes at that temperature, was further raised to 260C over a period ofabout 1 hour while discharging the gas from the container. The reactionmixture was then heat-treated while keeping the EXAMPLE 7 4.16g of4-(3-aminopropoxy)phenyl-3-propylamine was dissolved in 40 ml ofdistilled water, and 332g of terephthalic acid was added thereto andheat-dissolved by heating in a water bath. The mixture was then allowedto stand to precipitate a white crystalline substance having a meltingpoint of 256C. The separated and dried substance was charged into apressure container and heat-treated in a nitrogen atmosphere in the samemanner as in Example 6 to give a polymer having the same quality as thatobtained in Example 6. The resulting polymer had an ninh. of 0.53.

The polymer thus obtained was then melt-spun through a single-holenozzle, and the resulting fibers were drawn to 4.91 times their originallength in a water bath at 60C and subjected to heat-treatment undertension to give fibers having a tensile strength of 2.18 g/den., 25percent elongation, and an initial modulus of elasticity of 416 Kg/mm.The equilibrium moisture-absorbability at percent relative humidity wasabout 6.0 percent (at 20C).

The same procedure as above was repeated using isophtalic acid in placeof terephthalic acid to give a colorless transparent polymer softeningat 126C.

EXAMPLE 8 mosphere and sealed. The container was then placed in an oilbath, and the temperature was raised slowly to 270C over a period of 4hours. After 2 hours at that temperature, the pressure in the containerwas reduced by discharging the gas. When the pressure was reduced to 30mmHg, the temperature was raised to 280C where the reaction mixture washeat-treated. The resulting polymer had an 1; inh. of 0.30.

EXAMPLE 9 9.05g of the polyamide intermediate obtained in Example 2 wasplaced in a flask having a glass side-arm equipped with a capillary forthe introduction of gas, and, after purging with nitrogen gas to make anitrogen atmosphere in the flask, the reaction was effected by immersingthe flask in an oil bath at 220i 5C for 5 hours under a slow stream ofnitrogen gas. At this point, the reaction mixture became viscous, and asample taken from the reaction mixture was a resinous substance havinghigh stiffness. In order to complete the reaction, the stream ofnitrogen gas was discontinued and the mixture was heated while keeping atemperature of 220C under a reduced pressure of about 30 mmHg for 2hours to give a milk-white, opaque resinous substance having highstiffness.

EXAMPLEYIO 10.47 of 4-(3-aminopropoxy)phenyl-3-propylamine was dissolvedin 500 ml of distilled water, and 15.14g of I the ground4,4'-dicarboxydiphenoxy-1,2-ethane was added thereto. After it washeat-dissolved on a water bath, the mixture was filtered while hot andallowed to cool to yield 16.0g of flake crystals having a meltingtemperature of 235 to 239C. 10.0g of the intermediate thus obtained wasplaced in a heat-resisting container which was then purged with nitrogengas to make a nitrogen atmosphere and sealed. After being heated at 240Cfor 2 hours, the pressure was gradually reduced by discharging the gasand further reduced to 1 mmHg where the reaction mixture was slowlyheated to 260C over a period of 1 hour while keeping the 1 mmHg pressureto give a white opaque polymer. The resulting polymer had a softeningpoint of 241 to 247C and a melting temperature of 267C in the form ofspherulite and showed an excellent melt-spinning property. The fibersobtained from the polymer by melt-spinning exhibited a remarkablyincreased strength after it was drawn on a heat-plate at a tem peraturehigher than 100C.

EXAMPLE l1 0.447g of the diamine, 0.6459g of 4,4-dicarboxydiphenoxyl,Z-ethane and 2 ml of distilled water were charged into a glass tube,and the mixture was slowly heated up to 240C over a period of 1 hour ina and the reaction mixture was then kept at 1 mmHg pressure and and 250Cfor a period of 30 minutes to give a white opaque resinous substance.The resulting polymer had substantially the same quality as thatobtained in Example 10.

EXAMPLE 12 6.00g of 4-(3-aminopropoxy)phenyl-B-propylamine was dissolvedin ml of water, and the resulting solution was mixed with 4.86g ofterephthalic acid followed by being heat-dissolved. The mixture was thenfiltered while hot, and the filtrate was allowed to stand to yield awhite crystalline precipitate of the polyamide intermediate. Theprecipitation can be promoted by the addition of methanol or ethanol ifit occurs too slowly. 0.464g of the thus obtained intermediate was thenplaced in a glass tube which was then sealed after purging with nitrogengas to make a nitrogen atmosphere. The tube was then placed in a siliconoil bath at 280C, and the temperature of the bath was increased to 297Cwhere the tube was opened. The pressure was then reduced to 5 mmHg wherethe reaction product was treated for 30 minutes. The resulting polymerwas light brown and opaque and had an ninh. of 0.40.

EXAMPLE l3 16.016g of the polyamide intermediate prepared in the samemanner as Example 12, 0.032g of adipic acid and 10.0 ml of water werecharged into a pressure'container which was then sealed after purgingwith nitrogen gas to make a nitrogen atmosphere. The container was thenplaced in an oil bath heated at 260C, and the temperature of the bath'was raised to 270C over a period of about 3 hours. After maintainingthat temperature for 15 hours, the inside pressure reached approximately25 Kg/cm. The pressure was then reduced slowly while keeping thetemperature of 270C over a period of about 3 hours followed by a furtherreduction to 30 mmHg where the reaction product was heated for anadditional 9 hours, the final temperature of the heating being 280C. Thepolymer thus produced was a brown and opaque/resin and had an inherentviscosity of 0.29.

We claim:

l. A linear film and fiber forming polyamide having a high glasstransition temperature composed essentially of randomly repeating unitshaving the formula:

and

wherein R is a member selected from the group consisting of aliphatic,aromatic and aliphatic-aromatic divalent radicals.

' t 4: 4: a a

